micro-XANES and micro-XRF investigations of metal binding mechanisms in biosolids

Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.     

Nitrogen and phosphorus status of soils and trophic state of lakes associated with forage-based beef cattle operations in Florida

Forage-based livestock systems have been implicated as major contributors to deteriorating water quality, particularly for phosphorus (P) from commercial fertilizers and manures affecting surface and ground water quality. Little information exists regarding possible magnitudes of nutrient losses from pastures that are managed for both grazing and hay production and how these might impact adjacent bodies of water. We examined the changes that have occurred in soil fertility levels of rhizoma peanut (Arachis glabrata Benth.)-based beef cattle pastures (n = 4) in Florida from 1988 to 2002. These pastures were managed for grazing in spring followed by haying in late summer and were fertilized annually with P (39 kg P2O5 ha(-1)) and K (68 kg K2O ha(-1)). Additionally, we investigated trends in water quality parameters and trophic state index (TSI) of lakes (n = 3) associated with beef cattle operations from 1993 to 2002. Overall, there was no spatial or temporal buildup of soil P and other crop nutrients despite the annual application of fertilizers and daily in-field loading of animal waste. In fact, soil fertility levels showed a declining trend for crop nutrient levels, especially soil P (y = 146.57 - 8.14 x year; r2= 0.75), even though the fields had a history of P fertilization and the cattle were rotated into the legume fields. Our results indicate that when nutrients are not applied in excess, cow-calf systems are slight exporters of P, K, Ca, and Mg through removal of cut hay. Water quality in lakes associated with cattle production was "good" (30-46 TSI) based on the Florida Water Quality Standard. These findings indicate that properly managed livestock operations may not be major contributors to excess loads of nutrients (especially P) in surface water.     

Greenhouse gas emissions from conventional, agri-environmental scheme, and organic Irish suckler-beef units

The problems of overproduction within the European Union countries and the environmental impact of agriculture have lead to the introduction of schemes that aim to reduce both. Beef (Bos taurus) production forms a large component of the Irish agricultural industry and accounts for more than one quarter of agricultural economic output. Recently, the European CAP (Common Agricultural Policy) has been re-evaluated to include supplementary measures that encompass the environmental role of agriculture rather than just the production role. A life cycle assessment (LCA) method was adopted to estimate emissions per kilogram of CO2 equivalent per kilogram of live weight (LW) leaving the farm gate per annum (kg CO2 kg(-1) LW yr(-1)) and per hectare (kg CO2 ha(-1) yr(-1)). Fifteen units engaged in suckler-beef production (five conventional, five in an Irish agri-environmental scheme, and five organic units) were evaluated for emissions per unit product and area. The average emissions from the conventional units were 13.0 kg CO2 kg(-1) LW yr(-1), from the agri-environmental scheme units 12.2 kg CO2 kg(-1) LW yr(-1), and from the organic units 11.1 kg CO2 kg LW yr(-1). The average emissions per unit area from the conventional units was 5346 kg CO2 ha(-1) yr(-1), from the agri-environmental scheme units 4372 kg CO2 ha(-1) yr(-1), and from the organic units 2302 kg CO2 ha(-1) yr(-1). Results indicated that moving toward extensive production could reduce emissions per unit product and area but live weight production per hectare would be reduced.     

Environmental and production consequences of using alum-amended poultry litter as a nutrient source for corn

Field trials were established to compare alum-treated poultry litter (ATPL), normal poultry litter (NPL), and triple superphosphate (TSP) as fertilizer sources for corn (Zea mays L.) when applied at rates based on current litter management strategies in Virginia. Trials were established in the Costal Plain and Piedmont physiographic regions near Painter and Orange, VA, respectively. Nitrogen-based applications of ATPL or NPL applied at rates estimated to supply 173 kg of plant-available nitrogen (PAN) ha(-1) resulted in significantly lower grain yields than treatments receiving commercial fertilizer at the same rate in 2000 and 2001 at Painter. These decreases in grain yield at the N-based application rates were attributed to inadequate N availability, resulting from overestimates of PAN as demonstrated by tissue N concentrations. However, at Orange no treatment effects on grain yield were observed. Applications of ATPL did not affect Al concentrations in corn ear-leaves at either location. Exchangeable soil Al concentrations were most elevated in treatments receiving only NH4NO3 as an N source. At N-based application rates, the ATPL resulted in lower Mehlich 1-extractable P (M1-P) and water-extractable soil phosphorus (H2O-P) concentrations compared to the application of NPL. A portion of this reduction could be attributed to lower rates of P applied in the N-based ATPL treatments. Runoff collected from treatments which received ATPL 2 d before conducting rainfall simulations contained 61 to 71% less dissolved reactive phosphorus (DRP) than treatments receiving NPL. These results show that ATPL may be used as a nutrient source for corn production without significant management alterations. Alum-treated poultry litter can also reduce the environmental impact of litter applications, primarily through minimizing the P status of soils receiving long-term applications of litter and reductions in runoff DRP losses shortly after application.     

Temporal and spatial distributions of sediment total organic carbon in an estuary river

Understanding temporal and spatial distributions of naturally occurring total organic carbon (TOC) in sediments is critical because TOC is an important feature of surface water quality. This study investigated temporal and spatial distributions of sediment TOC and its relationships to sediment contaminants in the Cedar and Ortega Rivers, Florida, USA, using three-dimensional kriging analysis and field measurement. Analysis of field data showed that large temporal changes in sediment TOC concentrations occurred in the rivers, which reflected changes in the characteristics and magnitude of inputs into the rivers during approximately the last 100 yr. The average concentration of TOC in sediments from the Cedar and Ortega Rivers was 12.7% with a maximum of 22.6% and a minimum of 2.3%. In general, more TOC accumulated at the upper 1.0 m of the sediment in the southern part of the Ortega River although the TOC sedimentation varied with locations and depths. In contrast, high concentrations of sediment contaminants, that is, total polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), were found in sediments from the Cedar River. There was no correlation between TOC and PAHs or PCBs in these river sediments. This finding is in contradiction to some other studies which reported that the sorption of hydrocarbons is highly related to the organic matter content of sediments. This discrepancy occurred because of the differences in TOC and hydrocarbon source input locations. It was found that more TOC loaded into the southern part of the Ortega River, while almost all of the hydrocarbons entered into the Cedar River. This study suggested that the locations of their input sources as well as the land use patterns should also be considered when relating hydrocarbons to sediment TOC.     

Soil organic carbon sequestration in cotton production systems of the southeastern United States: a review

Past agricultural management practices have contributed to the loss of soil organic carbon (SOC) and emission of greenhouse gases (e.g., carbon dioxide and nitrous oxide). Fortunately, however, conservation-oriented agricultural management systems can be, and have been, developed to sequester SOC, improve soil quality, and increase crop productivity. Our objectives were to (i) review literature related to SOC sequestration in cotton (Gossypium hirsutum L.) production systems, (ii) recommend best management practices to sequester SOC, and (iii) outline the current political scenario and future probabilities for cotton producers to benefit from SOC sequestration. From a review of 20 studies in the region, SOC increased with no tillage compared with conventional tillage by 0.48 +/- 0.56 Mg C ha(-1) yr(-1) (H(0): no change, p < 0.001). More diverse rotations of cotton with high-residue-producing crops such as corn (Zea mays L.) and small grains would sequester greater quantities of SOC than continuous cotton. No-tillage cropping with a cover crop sequestered 0.67 +/- 0.63 Mg C ha(-1) yr(-1), while that of no-tillage cropping without a cover crop sequestered 0.34 +/- 47 Mg C ha(-1) yr(-1) (mean comparison, p = 0.04). Current government incentive programs recommend agricultural practices that would contribute to SOC sequestration. Participation in the Conservation Security Program could lead to government payments of up to Dollars 20 ha(-1). Current open-market trading of C credits would appear to yield less than Dollars 3 ha(-1), although prices would greatly increase should a government policy to limit greenhouse gas emissions be mandated.     

Phosphorus and nitrogen in rainfall simulation runoff after fresh and composted beef cattle manure application

Fresh beef cattle (Bos taurus) manure has traditionally been applied to cropland in southern Alberta, but there has been an increase in application of composted manure to cropland in this region. However, the quality of runoff under fresh manure (FM) versus composted manure (CM) has not been investigated. Our objective was to compare runoff quality under increasing rates (0, 13, 42, 83 Mg ha(-1) dry wt.) of FM and CM applied for two consecutive years to a clay loam soil cropped to irrigated barley (Hordeum vulgare L.). We determined total phosphorus (TP), particulate phosphorus (PP), dissolved reactive phosphorus (DRP), total nitrogen (TN), NH4-N, and NO3-N concentrations and loads in runoff after one (1999) and two (2000) applications of FM and CM. We found significantly (P < or = 0.05) higher TP, DRP, and NH4-N concentrations, and higher DRP and TN loads under FM than CM after 2 yr of manure application. The TP loads were also higher under FM than CM at the 83 Mg ha(-1) rate in 2000, and DRP loads were higher for FM than CM at this high rate when averaged over both years. Application rate had a significant effect on TP and DRP concentrations in runoff. In addition, the slope values of the regressions between TP and DRP in runoff versus application rate were considerably higher for FM in 2000 than for FM in 1999, and CM in both 1999 and 2000. Significant positive relationships were found for TP and DRP in runoff versus soil Kelowna-extractable P and soil water-extractable P for FM and CM in 2000, indicating that interaction of runoff with the soil controlled the release of P. Total P and DRP were the variables most affected by the treatments. Overall, our study found that application of CM rather than FM to cropland may lower certain forms of P and N in surface runoff, but this is dependent on the interaction with year, application rate, or both.     

Mapping ground water vulnerability to pesticide leaching with a process-based metamodel of EuroPEARL

To support EU policy, indicators of pesticide leaching at the European level are required. For this reason, a metamodel of the spatially distributed European pesticide leaching model EuroPEARL was developed. EuroPEARL considers transient flow and solute transport and assumes Freundlich adsorption, first-order degradation and passive plant uptake of pesticides. Physical parameters are depth dependent while (bio)-chemical parameters are depth, temperature, and moisture dependent. The metamodel is based on an analytical expression that describes the mass fraction of pesticide leached. The metamodel ignores vertical parameter variations and assumes steady flow. The calibration dataset was generated with EuroPEARL and consisted of approximately 60,000 simulations done for 56 pesticides with different half-lives and partitioning coefficients. The target variable was the 80th percentile of the annual average leaching concentration at 1-m depth from a time series of 20 yr. The metamodel explains over 90% of the variation of the original model with only four independent spatial attributes. These parameters are available in European soil and climate databases, so that the calibrated metamodel could be applied to generate maps of the predicted leaching concentration in the European Union. Maps generated with the metamodel showed a good similarity with the maps obtained with EuroPEARL, which was confirmed by means of quantitative performance indicators.     

Iron and arsenic release from aquifer solids in response to biostimulation

Biostimulation has been used at various contaminated sites to promote the reductive dechlorination of trichloroethylene (TCE), but the addition of carbon and energy donor also stimulates bacteria that use Fe(III) as the terminal electron acceptor (TEA) in potential competition with dechlorination processes. Microcosm studies were conducted to determine the influence of various carbon donors on the extent of reductive dissolution of aquifer solids containing Fe(III) and arsenic. Glucose, a fermentable and respirable carbon donor, led to the production of 1500 mg Fe(II) kg(-1), or 24% of the total Fe in the aquifer sediment being reduced to Fe(II), whereas the same concentration of carbon as acetate resulted in only 300 mg Fe(II) kg(-1) being produced. The biogenic Fe(II) produced with acetate was exclusively associated with the solid phase whereas with fermentable carbon donors as whey and glucose, 22 and 54% of the Fe(II) was in solution. With fermentation, some of the metabolites appear to be electron shuttling chemicals and chelating agents that facilitate the reductive dissolution of even crystalline Fe(III) oxides. Without the presence of electron shuttling chemicals, only surficial Fe in direct contact with the bacteria was bioavailable, as illustrated when acetate was used. Regardless of carbon donor type and concentration, As concentrations in the water exceeded drinking water standards. The As dissolution appears to have been the result of the direct use of As as an electron acceptor by dissimilatory arsenic reducing bacteria. Our findings indicate that selection of the carbon and energy donor for biostimulation for remediation of chlorinated solvent impacted aquifers may greatly influence the extent of the reductive dissolution of iron minerals in direct competition with dechlorination processes. Biostimulation may also result in a significant release of As to the solution phase, contributing to further contamination of the aquifer.     

Spatiotemporal evolution of soil pH and zinc after the Aznalcollar mine spill

The residual pollution after the Aznalcóllar (southwestern Spain) pyrite mine spill is still a threat due to the continuing oxidation of sulfuric minerals. The objective of this paper was to analyze the combined effect of pyrite oxidation, sugar beet foam applications, and meteorological conditions on the spatiotemporal evolution of the pH and EDTA-extractable Zn concentration, using non co-located data from 11 sampling dates between June 1999 and March 2002. Median pH values ranged from 4.4 at the beginning of the monitoring period to 7.6 at the end, although values near 2.5 were observed throughout the entire period, despite of two sugar beet foam (SBF) applications. Zinc distributions were positively skewed and median concentrations ranged from 17 to 94 mg kg(-1). The inverse relationship between pH and Zn became weaker toward the end of the monitoring period as a consequence of the precipitation and posterior dissolution of newly formed minerals from the reaction products of the pyrite oxidation. Normal score maps showed that after the SBF applications only 0.5% of the monitored area was below the pH = 4 threshold, while on other dates up to one-third of the area remained below this value. The better performance of the second SBF application could be explained in terms of pyrite oxidation pathways and environmental conditions. From this analysis, with data obtained under uncontrolled field conditions, it is concluded that SBF should be applied before or during the wet and cold season to alleviate acidification, caused by the oxidation of pyrite or other sulfuric minerals.